Barrier film structures

ABSTRACT

Articles useful as RF-sealable packaging materials comprise a halopolymer barrier layer coated onto, or adhered to, a carbon monoxide-containing polymer, wherein the carbon monoxide-containing polymer provides RF-sealability to the structure. Other layers of materials may be employed as part of the packaging material.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of co-pending applicationSer. No. 645,990 filed Aug. 31, 1984, now U.S. Pat. No. 4,601,948, whichis, itself, a continuation-in-part of copending Ser. No. 531,110 filedSept. 12, 1983, now U.S. Pat. No. 4,600,614.

FIELD OF THE INVENTION

Multi-ply packaging materials, having good barrier properties, which aresealable with high-frequency electromagnetic energy.

BACKGROUND OF THE INVENTION

The use of high-frequency electromagnetic energy as a means of heatingpolymers is an advancing art which finds application in many fields,especially in fields in which conventional conductive, convective, orradiant heat energy is either not suitable, not practical, or notpossible. For instance, sealing of a polymer to itself or to some othersubstrate can be (if the composition of the polymer is appropriate) animportant commercial technique in producing a desired end-product.

There are some polymers which are not suitable, or at least notwell-suited, for high-frequency heating operations. In such ill-suitedpolymers high-frequency heating either does not occur, or if it occursit does so only after inefficiently prolonged periods of treatment time.In production assembly lines, e.g., a quick heat-seal operation isgenerally preferred over a prolonged heat-seal operation.

Among the polymers which are ill-suited for high-frequency heating areolefin polymers, e.g., polymers and copolymers of ethylene, propylene,styrene or other α-olefinically unsaturated hydrocarbons having about 2to about 10 carbon atoms. Some of these olefin polymers may containpolar groups, or polarizable groups, due to the incorporation thereinof, e.g., acrylic (or methacrylic) acids or their alkyl esters ascomonomers with the olefins, and these groups may, at high levels ofincorporation tend to impart a modicum of high-frequency heatability tothe polymer, but the efficacy is generally so slight that it isinfeasible on a commercial basis. Some polymers having polar groups,e.g. chlorinated P.E., ethylene/vinyl acetate copolymer, PVC,polyvinylidene chloride, and polyamide, are heatable under the influenceof certain frequencies of electromagnetic radiation, but are notgenerally well-suited for bonding using the higher frequencies.

Polyethylene is particularly known in the art to be substantiallyunsuitable for high-frequency heating unless sensitizers are added tothe polymer; this is true regardless of whether it is linear orbranched, or of whether it is low, medium, or high density (see, e.g.,U.S. Pat. Nos. 3,336,173; 3,640,913; and 3,810,799).

It is an object of the present invention to provide ways and means forimparting improved high-frequency heatability to those olefin polymersand copolymers which ordinarily are found to be ill-suited for suchheating operations, wherein carbon monoxide-containing olefin polymersare prepared and provided with a barrier film of a polymer havinghalogen groups pendant from the polymer chain.

SUMMARY OF THE INVENTION

Films, sheets, or slabs of olefin polymers containing carbon monoxidecopolymerized therein are coated, on at least a portion thereof, with afilm having good barrier properties, such as polyvinyl halide,polyvinylidene halide, and copolymers comprising polyvinyl halide andpolyvinylidene halide; the halide is preferably chloride, but may befluoride, or a mixture of chlorides and fluorides may be used.

DETAILED DESCRIPTIONS

The preparation of olefin polymers, copolymers, and terpolymers is wellknown and the methods and techniques are well known to practitioners ofthe relevant polymer art. For the most part, the olefin copolymers andterpolymers of interest in this present disclosure are prepared by thewell known high pressure, high temperature, free-radical initiated,polymerization method such as the historically-popular ICI process orsuch as disclosed in U.S. Pat. No. 2,497,323. However, thosepolymerization processes which employ certain of the coordinationcatalysts or metal catalysts (e.g., the well-known Ziegler-type,Natta-type, or Phillips-type) may be used by selecting a catalyst (suchas in U.S. Pat. No. 3,083,184) which is not easily poisoned ordeactivated by carbon monoxide, or other oxygen-containing monomer,which is generally highly reactive with many metal-carbon bonds.

Olefin polymers within the purview of this invention, and which arerendered heatable (by high-frequency electromagnetic radiation) byincorporating carbon monoxide groups into the polymer chain, arepolymers formed by polymerizing monomers having ethylenic (olefinic)unsaturation. A sole olefin or a plurality of olefins may be used alongwith the carbon monoxide in preparing the polymers. Preferably theolefin monomer is ethylene (sometimes including a small proportion of aC₃ -C₈ aliphatic olefin for property modification). The olefin monomercan also include an unsaturated organic acid having 3 to 8 carbon atoms,such as acrylic acid, methacrylic acid, 1-butenoic acid, and the like;alkyl esters or metal salts of these acids may also be used, such asethyl acrylate, methyl methacrylate, 2-ethyl hexyl acrylate, sodiumacrylate, potassium methacrylate, and the like. HydrogenatedCO-containing olefin polymers (which creates H--C--OH groups along thepolymer chain) are included here, such as hydrogenated ethylene/carbonmonoxide copolymers. U.S. Pat. No. 2,495,292 discloses methods ofhydrogenating such CO groups in a polymer chain.

It has been known for many years that olefins, e.g. ethylene, and carbonmonoxide, can be copolymerized or terpolymerized.

The following listed patents are believed to be representative of theart pertaining to interpolymers of carbon monoxide and monoolefins: U.S.Pat. Nos. 2,495,292; 2,495,286; 2,497,323; 2,641,590; 3,083,184;3,248,359; 3,530,109; 3,676,401; 3,689,460; 3,694,412; 3,780,140;3,835,123; 3,929,727; 3,948,832; 3,948,873; 3,948,850; 3,968,082;3,984,388; 4,024,104; 4,024,325; 4,024,326; 4,139,522; 4,143,096;4,304,887; and Canadian No. 471,169.

It is also known that there are additives (sensitizers) which can beblended into a polymer, e.g. polyethylene, to render it heatable byelectromagnetic high-frequency energy, such as talc, ZnCl₂, carbonblack, nylon, iron oxide, and others. Such additives, however, usuallyhave a pronounced visual, physical, or chemical effect which, in someapplications, is desirably avoided. Furthermore, when using additives assensitizers one is faced with having to obtain a uniform distribution ofthe sensitizers in order to avoid "hot-spots" which can give irregularresults and may even damage the polymer.

It is within the purview of one aspect of the present invention conceptto create high-frequency sensitizer groups along the polymer chain inpolymers which otherwise would be ill-suited for high-frequency heating.In this invention one does not encounter untoward visual effects in thepolymer as a result of the sensitizer. Even in the present embodimentswherein a polymer of the present invention is blended with polymer(e.g., as a "masterbatch") in order to sensitize the whole, the polymersare generally compatible to an extent at which little or no visualeffects are encountered. Thus, clear films of olefin polymers can beprepared, in accordance with the present invention, which are readilyheat-sealed using high-frequency energy. It is especially of importancethat the present invention provides polymers which are heatable by theaction of microwave (MW) energy, a particular portion of thehigh-frequency energy range, thereby helping to fill a need in theindustry where there is a sparsity of polymers which are suitable. Theamount of CO groups in the ethylene interpolymers should be in the rangeof about 0.1 to about 50% by weight, preferably about 1 to about 40% byweight, most preferably about 5 to about 30% by weight.

As used herein "high-frequency sealability" refers to the bonding of thesealable polymer to a portion of itself or to another material usingelectromagnetic energy frequencies of 0.1-30,000 MHz. This includesradio-frequency (RF) heating and microwave (MW) heating incontradistinction to conventional heat sealing. The high-frequency rangeis generally taken to include electromagnetic waves over a broadfrequency range (0.1 to 30,000 MHz) and covers the radio frequency (RF)range (1 MHz-300 MHz), and the microwave (MW) frequency range (300MHz-10,000 MHz). The RF and MW ranges are of particular interest here,with special interest in the MW range due to the increasing use of MW asa processing device.

Uses for this technology (polymer or blends) includes packagingapplications where high speed and/or non-destructive seals are required,e.g., high-frequency activated adhesive films; extrusion coatings;moldings; hot melts in uses such as aseptic packaging, retort pouches,sandwich bags; lamination of foam, fabric, or film layers; powdermoldings, and the like. Furthermore, the present invention providespolymers suitable for use in RF extruders, including continuousextruders or batch extruders. Wire and cable coatings can be applied ina continuous RF-extruder by the present invention.

In one aspect, this invention relates to an improved method of renderinga polymer which is not heatable or sealable utilizing high-frequency(0.1-30,000 MHz) electromagnetic radiation (HF) (e.g., polyethylene,polypropylene, polystyrene, etc.) HF-sealable by either incorporation ofcarbon monoxide by copolymerization or by blending or grafting a carbonmonoxide copolymer or terpolymer into the polymer matrix. Hydrogenatedforms of the above can also be used. In addition, ethylene/carbonmonoxide copolymer (ECO) and interpolymers containing CO can be used formicrowave sealing applications (i.e., microwave sealable plastic bags,toothpaste tube sealing, shampoo tube sealing, other microwave sealablecontainers, valve bag sealing, etc.). We have unexpectedly found thatECO copolymers and interpolymers convert high-frequency electromagneticradiation into heat for sealing, welding or fusing over a broadfrequency range (0.1-30,000 MHz). Typically, ethylene copolymers may beheatable to some extent at low RF frequencies of 1-50 MHz (radiofrequency range is typically considered to be from 1-300 MHz; microwavefrequency range is 300-30,000 MHz) such as ethylene/vinyl acetatecopolymer (EVA), but none have been found which efficiently heat at thehigher frequencies. Other examples of polymers heatable at lowfrequencies, but which do not efficiently heat at the higher frequenciesare polyvinyl chloride (PVC), polyvinylidene chloride, chlorinatedpolyethylene (CPE), and Nylon 6.

The advantages of sealing polymers with high-frequency electromagneticwaves include faster and more efficient sealing, sealing through poorheat-conductors, e.g., paper or cardboard exteriors, stronger seals orbonds, improved economics based on efficient use of energy input, theability to seal, bond, or laminate larger surface areas, sealing ofthicker or more complex film laminates, specific sealing, and theability to seal wet surfaces at microwave frequencies where moisturecouples with the energy to provide heat for the bonding.

The general heating rate for the interaction of an electromagnetic wavecan be used to determine sealing rates utilizing the following equation:

    G=13.3×10.sup.-14 fF.sup.2 (E' tan δ)          (1)

where G is the heating rate in cal/cm³.sec, f is the frequency in Hz ofthe electromagnetic wave, F² is the field strength or power in volts/cm,E' is the dielectric constant of the polymer and tan δ is the dielectricloss tangent (measure of the heating property of the material whenexposed to HF electromagnetic waves). Thus, in general (since tan δvaries with frequency) the higher the frequency the higher the heatingrate or the faster the sealing ability of the material. The carbonmonoxide (CO) containing interpolymers can be sealed or heated over abroad frequency range which allows one to have the option of usingmicrowave frequencies for optimum speed in heating or sealing. Thisfeature (heating or sealing over such a broad frequency) appears to beunique to these interpolymers or copolymers containing CO.

There are also advantages of CO copolymers or interpolymers over otherpolymers (e.g., PVC, PVDC, CPE, EVA), that are sealable using radiofrequency sealing methods which include, for example:

1. ECO is like conventional low density polyethylenes in physicalproperties and film appearance, i.e., higher melting point, low filmblockage, easy processability, can be used for film, extrusion coatingand molding resin. Furthermore, the need for plasticizers is obviated.

2. CO can be copolymerized with ethylene and vinyl acetate to produce aCO-modified EVA polymer to render it more sealable and broadens thesealing frequency range. CO can also be copolymerized into an EAA orEMAA polymer allowing an EAA-like or EMAA-like terpolymer to be RF andmicrowave sealable (EAA and EMAA are not RF or microwave sealable). Thisincludes the metal salts or "ionomer-type" embodiments of thesepolymers.

3. CO containing copolymers or interpolymers have higher dielectricconstants than EVA copolymers, allowing higher field strengths to beused without the fear of arcing.

EXAMPLE 1

The following Table I shows the time required to melt a polymer in amicrowave oven (Sears Microclassic microwave oven) at maximum power(brought 275 ml of water to boil in 2.48 minutes).

                  TABLE I                                                         ______________________________________                                                                   Melt Time                                          Resin*            MI***    (sec)**                                            ______________________________________                                        ECO                                                                           10% CO            1        37                                                 10% CO            10       35                                                 5% AA; 10% CO     10       75                                                 5% AA; 10% CO     3.5      85                                                 5% AA; 5% CO      3        90                                                 1% CO             1        90                                                 EVA (14% VA)      wax      >10 min                                            EAA (12% AA)      wax      >10 min                                            Oxidized (PE)     wax      >10 min                                            E/vinyl alcohol   --       42                                                 EVA/CO (20% CO)   --       25                                                 EVA                                                                           28% VA            3.5      >10 min                                            18% VA            3.0      >10 min                                            EAA                                                                           20% AA            300      >10 min                                            30% AA            1250     >10 min                                            HDPE (0.965 dens.)                                                                               .8      >10 min                                            LDPE (0.918 dens.)                                                                              6        >10 min                                            LLDPE (0.918 dens.)                                                                             6        >10 min                                            6 resin (dried)   --       >10 min                                            Saran ® B-200 polymer                                                                       --       >10 min                                            Chlorinated P.E.  --       >10 min                                            ______________________________________                                         *Samples were 2" discs of 60 mil thickness, positioned on a nonRF             sensitive polycarbonate sheet.                                                **If no melting was evident in 10 minutes, the test was stopped and           reported as > 10 min.                                                         ***MI is melt index in accordance with ASTM D1238.                             ®Registered tradenames                                              

As can be seen from Table I, only ethylene/vinyl alcohol polymer andethylene interpolymers containing carbon monoxide melted in themicrowave oven (2450 MHz).

EXAMPLE 2

In order to determine the RF-sealability of carbon monoxide containingcopolymers, a Callanan 11/2 KW high-frequency electronic generatorequipped with a 3/32"×12" brass sealing electrode and operating over afrequency range of 20-40 MHz (RF) was utilized in the following sealingexperiment. Samples of 3 mil blown film of the copolymers shown in TableII were attempted to be sealed using the above RF sealer utilizingvarious dwell settings (sealing time) and power settings. The seals wereexamined and a seal was considered to have been made when the two sheetsof material could not be separated at the seal point without tearingeither piece of film. Table II also shows the improvement in minimumsealing time and resistance to arcing of CO containing copolymers incomparison to EVA copolymers.

                  TABLE II                                                        ______________________________________                                        RADIO FREQUENCY SEALABILITY                                                                 Power    Dwell Time                                             Resin         Setting  sec.       Sealability                                 ______________________________________                                        EVA           90       3          No                                          (9.3% VA, 2 MI)                                                                             100      3          No                                                        100      4           Arc*                                       EVA           10       1          No                                          (18% VA, 2.5 MI)                                                                            40       2          No                                                        70       2          Yes                                                       60       2          Yes                                                       70       1          No                                                        80       1          Yes                                                       90       2          Arc                                         EVA           60       2          No                                          (12.0% VA, 2.5 MI)                                                                          70       2          No                                                        80       2          No                                                        90       2          Yes                                                       100      1          Arc                                         EVA           30       2          Yes                                         (25% VA, 2 MI)                                                                              20       2          No                                                        60       1          Yes                                                       60       .5         No                                                        70       .5         No                                                        80       .5         Arc                                         EVA           40       2          Yes                                         (28% VA, 3.0 MI)                                                                            20       1          Yes                                                       70       .5         Yes                                                       80       .25        Arc                                                       80       .5         Arc                                         ECO           50       2          No                                          (10% CO, 1 MI)                                                                              60       2          No                                                        70       2          Yes                                                       100      1          Yes                                                       90       1          Yes                                                       80       1          No                                                        100      .5         Yes                                                       90       .5         No                                          E/AA/CO       70       2          Yes                                         (5% AA, 10% CO,                                                                             60       2          Yes                                         3.5 MI)       50       2          Yes                                                       70       1          Yes                                                       60       1          Yes                                                       70       .5         Yes                                                       60       .5         No                                                        80       .25        No                                                        90       .25        Yes                                         E/AA/CO       70       .5         Yes                                         (5% AA, 10% CO,                                                                             80       .5         Yes                                         10 MI)        80       .25        No                                                        90       .25        Yes                                         ______________________________________                                         *Arc results in a hole burned through the film.                          

Within the purview of the present invention, useful articles areprepared which utilize the high-frequency electromagnetic radiationheatability and sealability of the above described CO containing olefinpolymers. Layers or plies of these polymers are used as a means forsealing or bonding materials which are not, themselves, efficientlysuitable for high-frequency electromagnetic radiation sealing orbonding. Various substrates, including particles, films, sheets, blocks.rods, spheres, and the like can be coated, at least in the area desiredto be bonded, with these subject polymers and then sealed or bondedtogether using high-frequency electromagnetic radiation, especiallythose frequencies in the microwave range. These polymers, in the form ofpowders or particles, may be extruded into useful shapes, or as coatingsonto other materials (e.g. wire and cable coatings), usinghigh-frequency electromagnetic radiation as the heating means.

Novel adhesives comprising terpolymers of ethylene/carbonmonoxide/carboxylic acid are prepared as embodiments in accordance withthe present invention. The carboxylic acid moiety of the terpolymer maybe any of the unsaturated carboxylic acid which are polymerizablethrough the double-bond, such as acrylic acid, methacrylic acid,crotonic acid, 1-butenoic acid, and the like, especially acrylic acid ormethacrylic acid, most especially acrylic acid, including salts of theseacids, such as metal salts, especially Na or K salts, commonly known as"ionomer" salts. The preparation of these E/CO/acid terpolymers may bedone in the same manner as the E/acid copolymers as disclosed in U.S.Pat. No. 3,520,861 and U.S. Pat. No. 4,351,931. These patents disclosethe use of a high pressure stirred autoclave reactor, using afree-radical initiator, to prepare uniform, random ethylene/carboxylicacid copolymers. Whereas these terpolymers can also be made by graftingtechniques, by block polymerization techniques, in batch reactors, or inlong tube reactors, it is preferred that the above disclosed stirredautoclave reactors be used whereby substantially uniform, randomterpolymers are made.

Even though E/AA copolymers are generally regarded as having goodadhesive properties with many substrates, as compared to polyethylene,there are some substrates where improved adhesion is desirable. Notableamong these substrates, where improved adhesion is desirable, arepolyamides (e.g. nylons), polyolefins (e.g. LDPE, HDPE, LLDPE, PP, OPP,polyisoprene), fluoropolymers (e.g. PTFE), polyethylene terephthalate(PET), metals (e.g. steel and aluminum foil), some paper-type products(e.g. glassine, kraft paper, etc.), cured epoxy resins, ethylene/vinylalcohol copolymers, cured novolac resins, polyurethanes, polycarbonates,chloropolymers (e.g. polychloroprene, PVC, polyvinylidene), andinorganic substrates (e.g. glass and porcelain).

Conversely, whereas ECO copolymers exhibit a modicum of heat-activatedor heat-induced adhesive properties to some substrates, it has beendetermined that the present E/CO/acid terpolymers exhibit greateradhesiveness in such instances, especially to such substrates as SARANpolymer and polycarbonate (where ECO has some adhesiveness) and toethylene/vinyl alcohol copolymers, nylon, and aluminum (where ECOexhibits little or no adhesiveness).

The adhesive properties of these E/CO/acid terpolymers may be utilizedby any convenient method, such as by hot-melt application, bypost-heating of the adhesive in-situ on the substrate, by application ofthe adhesive in a carrier, such as in a solvent or as a dispersion in anaqueous carrier or in a non-solvent. The adhesive may be used in joiningsubstrates of similar or dissimilar materials. As mentionedhereinbefore, these terpolymers are also suitable for use as films or asother materials and have the beneficial property of being high-frequencyheatable, especially at those frequencies which are in, or near, themicrowave range.

These E/CO/acid terpolymers are quite similar in optics and physicalproperties to EAA copolymers made by the same process. Insofar as thesenovel adhesive terpolymers are concerned, the ranges of the comonomeringredients are as follows:

    ______________________________________                                        Weight % of Terpolymer                                                                                         Most                                         Monomer      Operable   Preferred                                                                              Preferred                                    ______________________________________                                        Ethylene     20-98      40-98    60-96                                        Carbon Monoxide                                                                            1-40       1-30     2-20                                         Carboxylic Acid                                                                            1-40       1-30     2-20                                         ______________________________________                                    

The melt index (M.I.), also called melt flow rate, as measured inaccordance with ASTM D-1238, is preferably in the range of about 0.5 toabout 2500, most preferably in the range of about 1 to about 60, evenmore preferably in the range of about 1 to about 20.

These E/CO/acid terpolymers are thermoplastic and can be thermoformedinto films, sheets, tubes, or other articles. Powders of theseterpolymers can be compression molded into sintered forms or the powderscan be applied to the surface of a substrate where it can beheat-plastified to provide an adhesive layer or coating on the substrateor between two substrates. A film, strip, or sheet of these terpolymerscan be placed between two substrates and heat-plastified to serve as anadhesive or laminate layer to hold the substrates together.

The following examples illustrate certain embodiments of the E/CO/acidterpolymers, compared with other polymers, but the invention is notlimited to the specific embodiments shown.

EXAMPLE 3

The examples shown in Table III below are produced by compressionmolding at pressures and temperatures conducive to heat fusion. Theresin samples to be tested for adhesion are first compression moldedinto 20 mil plaques and then laminated to the substrate (a film orplaque) to test for adhesion to the substrate. The adhesion ofethylene/carbon monoxide/acrylic acid terpolymers, E/CO/AA, is shown incomparison to low density polyethylene, LDPE; ethylene/acrylic acidcopolymer; E/AA; ethylene/vinylacetate copolymer, E/VA; ethylene/carbonmonoxide copolymer, E/CO; and ethylene/carbon monoxide/vinyl acetateterpolymer, E/CO/VA. The good adhesiveness obtainable with E/CO/AAterpolymers to the various substrates is evident, especially with nylon(a polyamide) and with polycarbonate which generally do not form strongbonds with most heat-plastified adhesives.

                                      TABLE III                                   __________________________________________________________________________    COMPRESSION MOLDED ADHESION VALUES (lbs/in)                                               PERCENT                                                                       COMONOMER                                                                     WITH ETHYLENE                                                                             SUBSTRATE                                             ADHESIVE    AA CO VA MI A.sup.1                                                                           B.sup.2                                                                          Nylon.sup.3                                                                       Aluminum.sup.4                                                                      EVAL.sup.5                                                                         Polycarbonate.sup.6             __________________________________________________________________________    LDPE        -- -- -- -- .01 .01                                                                              .01 .05   .01  .01                             E/AA Copolymer                                                                            6.2                                                                              -- -- 3.02                                                                             .01 .02                                                                              2.4 18.1  .50  .05                             E/AA Copolymer                                                                            9.8                                                                              -- -- 9.6                                                                              .01 .01                                                                              3.8 29.2  .70  .08                             E/AA Copolymer                                                                            9.0                                                                              -- -- 3.6                                                                              .01 .01                                                                              4.2 27.4  .50  .08                             E/VA Copolymer                                                                            -- -- 28.5                                                                             5.8                                                                              7.5 6.3                                                                              5.4 2.1   3.1  .08                             E/VA Copolymer                                                                            -- --  6.5                                                                             1.11                                                                             .04 .10                                                                              6.44                                                                              8.9   6.8  .05                             E/CO/AA Terpolymer                                                                        5.0                                                                              5.0                                                                              -- 56.1                                                                             J10.47                                                                            J2.39                                                                            1.83                                                                              18.0  3.1  7.5                             E/CO/AA Terpolymer                                                                        5.0                                                                              10.0                                                                             -- 4.3                                                                              11.8                                                                              J1.89                                                                            9.88                                                                              16.0  7.5  J10.4                           E/CO/AA Terpolymer                                                                        5.0                                                                              10.0                                                                             -- 18.7                                                                             9.0 J4.2                                                                             J23.2                                                                             22.5  7.9  J10.4                           E/CO Copolymer                                                                            0  10.0                                                                             -- 7  9.6 J2.4                                                                             .5  .4    .2   J7.8                            E/CO Copolymer                                                                            0  10.0                                                                             -- 8.2                                                                              10.3                                                                              J4.1                                                                             .1  .8    .5   J8.2                            E/CO/AA Terpolymer                                                                        10.0                                                                             5.0                                                                              -- 4.1                                                                              7.1 1.5                                                                              J24.2                                                                             24.9  6.9  DNR                             E/CO/VA Terpolymer                                                                        -- 10.0                                                                             10.0                                                                             35.2                                                                             8.2 6.1                                                                              8.8 2.0   1.33 DNR                             __________________________________________________________________________     J indicates cohesive failure strength of film substrate                       A.sup.1 6mil SARAN PVDC film                                                  A.sup.2 2mil SARAN PVDC film                                                  .sup.3 Nylon6 film                                                            .sup.4 Aluminum                                                               .sup.5 ethylene/vinyl alcohol copolymer, molded 20mil plaque                  .sup.6 2mil polycarbonate cast film                                      

EXAMPLE 4

In order to compare an ethylene/carbon monoxide copolymer (10% CO byweight, 18.7 M.I.) with an ethylene/carbon monoxide/acrylic acidterpolymer (10% CO and 5% AA by weight, 12.8 M.I.), a 2-mil thickcoating of each is extrusion-coated onto various substrates and adhesion(lb./in.) is measured. In Table IV below, Sample A is the E/CO copolymerand is extrusion-coated at about 300° C.; Sample B is the E/CO/AAterpolymer and is extrusion-coated at about 290° C.; PVDC meanspolyvinylidene chloride; EVAL means ethylene/vinyl alcohol copolymer;LLDPE means linear low density polyethylene; LDPE means low densitypolyethylene; PET means polyethylene terephthalate; OPP means orientedpolypropylene.

                                      TABLE IV                                    __________________________________________________________________________    SAMPLE                                                                              PVDC                                                                              PET                                                                              POLYAMIDE                                                                             OPP ALUMINUM                                                                              LDPE                                                                              LLDPE                                    __________________________________________________________________________    A     >5* 0.5                                                                              0.32    <0.05                                                                             0.14    0.3 0.07                                     B     >5* 1.6                                                                              2.44    0.05                                                                              2.5     0.5 0.5                                      __________________________________________________________________________     *All > samples resulted in film failure, not adhesive failure. The above      illustrates the superior adhesiveness of E/CO/AA terpolymers as compared      to E/CO copolymers.                                                      

EXAMPLE 5

The packaging industry utilizes a number of barrier resins, such as inTable V below, and the E/CO/acid terpolymers are found to make goodadhesives for making laminates which contain one or more barrier layers.

                  TABLE V                                                         ______________________________________                                        Oxygen Barrier Resistance                                                     Nominal Value*                                                                            Polymer                                                           ______________________________________                                        0.03-0.30   ethylene/vinyl alcohol copolymers; EVAL                           0.05-0.20   polymers or copolymers based in vinyl                                         chloride and/or vinylidene chloride                                           monomers; SARAN polymers                                           2          polyvinyl chloride, PVC                                           80          plasticized PVC                                                    4          PET, polyethylene terephthalate                                   10          nylon, polyamide                                                  125         HDPE, high density polyethylene                                   ______________________________________                                         *cm.sup.3 of O.sub.2 as measured by ASTM D1434.                          

EXAMPLE 6

It has been determined that E/CO/acid terpolymers are useful asheat-plastified adhesives between layers of similar plastics or resins,layers of dissimilar plastics or resins, and/or between layers ofplastics or resins and completely different substrates, such as paper,cloth, metal, glass, vitreous material, wood, leather. These terpolymersare also useful as heat-plastified adhesives between layers ofmaterials, neither layer being plastic or resin, such as the materialsnamed immediately above.

Particularly useful embodiments are those wherein a CO-containingpolymer, especially an E/CO, E/CO/VA, E/CO/MAA, or E/CO/AA polymer isemployed as an RF-sealable layer laminated, or otherwise adhered, to abarrier film of a halo-polymer such as polyvinyl halide, polyvinylidenehalide, copolymers of polyvinyl halide and polyvinylidene halide,halogenated polyolefins, halogenated polyethylene, and the like, wherethe halogen groups are preferably chlorine or fluorine or a mixture ofchlorine and fluorine; most preferably the halogen is chlorine. Layersof other materials may be used as parts of a multi-layered structurewhich include the halo-polymer barrier layer on a CO-containing polymer,especially an E/CO, E/CO/VA, E/CO/MAA, or E/CO/AA polymer RF-sealablelayer, including those where the E/CO, E/CO/VA, E/CO/MAA, or E/CO/AApolymer is co-extruded with other polymers. The halo-polymer may beextruded onto the E/CO, E/CO/VA, E/CO/MAA, or E/CO/AA polymer layer, ormay be co-extruded with the E/CO, E/CO/VA, E/CO/MAA, or E/CO/AA polymeror may be applied as a fine-particle aqueous dispersion, such as alatex, or as a solution, thereby forming a thin film on the E/CO,E/CO/VA, E/CO/MAA, or E/CO/AA. The barrier properties of greatestconcern for many packaging films are those wherein O₂ and H₂ O aresubstantially prevented from passing through the packaging film by theuse of a barrier layer in, or on, the packaging film.

The halopolymers may also contain other copolymerized monomer moieties,such as acrylate, methacrylate, acrylonitrile, and the like, such as:poly(vinylidene chloride)/vinyl chloride; poly(vinylidenechloride)/acrylonitrile; poly(vinylidene chloride)/acrylate;poly(vinylidene chloride)/alkyl methacrylate; poly(vinylidenechloride)/methyl methacrylate; and terpolymers of these.

Latexes (aqueous fine dispersions) of polyvinylidene chloride and/orpolyvinyl chloride which are suitable for coating of the E/CO, E/CO/VA,E/CO/MAA, and E/CO/AA polymers have solids contents generally in therange of 10-90 wt.%, preferably about 30 to about 75 wt.% and generallycontain surfactants, stabilizers, and/or surface tension modifiers, andgenerally have surface tensions in the range of about 30 to 90 dynes/cm,preferably about 40 to 80 dynes/cm when measured at 23° C.

Latexes available commercially as SARAN* latexes (*a tradename of TheDow Chemical Company) may be used, such as, SL112, SL116, SL118, SL143and SL159, all of which are latexes comprising vinylidene chloridepolymers which are commercially available.

Adhesion of the halo-polymer to the E/CO, E/CO/VA, E/CO/MAA, and E/CO/AAfilms, when applied as a latex (fine-particle aqueous dispersion), isappreciably improved by first treating the CO-containing film surfacewith a corona discharge. This corona treatment "cleans" the filmsurface, increases the polarity of the surface, and modifies the surfacetension of the film surface. Corona treatment is provided by using acommercially available apparatus, Model RS-96 Surface Treater from ENIPower Systems Inc. Treating levels of about 0.1 to about 20 watts/ft.²/min. (215 watts/m² /min.), preferably about 2-10 watts/ft.² /min. (21.5watts/m² /min. to about 107 watts/m² /min.) may be used. Above about 20watts/ft.² /min. (215 watts/m² /min.), one may encounter excessivepolymer degradation.

The latex may be applied to the film by spraying, brushing, orspreading, using a doctor blade or other device, if needed, to attainthe desired thickness, allowing for evaporation of the aqueous carrier.One type of spreader which functions as a "doctor blade" which has beencommonly used for many years in the art of laying down coatings on asubstrate, is a Mayer* rod (*a tradename) which is a round rod wrappedwith wire; these come in different sizes commensurate with the desiredthickness of the fluid latex to be applied. One may use a directgravier, a flexographic, offset gravier, or trailing blade coater toapply the latex. The latex is then dried, especially at about 2°-150° C.and can be heated using RF-heating frequencies.

Among the many possible laminates which comprise or contain aCO-containing polymer with a coating of halo-polymer on it, a fewparticular ones are illustrated, below:

    ______________________________________                                        halo-polymer                                                                            halo-polymer                                                                             halo-polymer                                                                              halo-polymer                                 CO-polymer                                                                              CO-polymer CO-polymer  CO-polymer                                             adhesive   adhesive    print                                                  barrier layer                                                                            barrier layer                                                                             halo-polymer                                           adhesive   adhesive                                                 halo-polymer                                                                            polyolefin paper                                                    CO-polymer           polyolefin  halo-polymer                                 adhesive             print       CO-polymer                                   polystyrene                                                                             halo-polymer                                                                             polyolefin  polycarbonate                                          CO-polymer                                                                    substrate                                                           ______________________________________                                    

In the above-illustrated layered structures the meaning of the termsused in describing the layers are:

halo-polymer--a thermoplastic organic polymer which contains sufficienthalogen groups to provide barrier properties to substantially inhibit orprevent the passage of O₂ or H₂ O; preferably these are polymersprincipally based on vinyl halide or vinylidene halide, where the halideis chloride or fluoride, or a mixture, most preferably chloride;

CO-polymer--a thermoplastic organic polymer having carbon monoxide unitsalong the polymer chain, preferably E/CO, E/CO/VA, E/CO/MAA, or E/CO/AA,most preferably E/CO or E/CO/AA;

adhesive--a thermoplastic (such as an acrylic or vinyl polymer) or athermosetting polymer or resin (such as a urethane or epoxy) which maybe used in providing adhesion of one layer to another, if needed;

barrier layer--this may be a halo-polymer as described above, or may beanother material which has desired barrier properties, such aspolyvinylalcohol, metal foil, nylon, polytetrafluoroethylene,polyethylene/vinyl alcohol copolymer, acrylonitrile polymers andcopolymers, and the like;

paper--this may be Kraft paper or other pressed fibrous material such asthose prepared in a Fourdrinier process;

print--this may be any printed matter, such as words, numbers, logos,designs, etc. which may be printed on at least one ply of a laminate;

substrate--this may be a layer of natural material, such as cloth,cellulosicbased, wood, metal, ceramic, or refractory material, or may bea synthetic material such as thermoplastic or thermosetting materials orpolymeric condensates, including sintered, woven, non-woven, cast, orfused materials; this includes, inter alia, HDPE, LLDPE, LDPE,polypropylene, other polyolefins, polyacrylates, vinyl polymers, and thelike.

Thin layers of halo-polymers are likely to emit heat about as fast as itis generated by RF-energy, thus thin layers are not efficiently broughtto a heat-plastified condition well enough to obtain a good seal, eventhough thin layers of the halopolymers provide good barrier propertiesfor the heat-sealable CO-containing polymer.

EXAMPLE 7

A 2-mil (0.05 mm) film of ECO polymer (containing 10% CO, 2 M.I.) wasproduced using a Sterling* blown film unit (*a tradename) having an8-inch (20.32 cm) die with a 3.5 inch (8.89 cm) extruder, L/D=30/1,operated at 425° F. (˜226.6° C.). The film was corona treated at atreatment level of 5 watts/ft² (53.7 watts/m² /minute). The surfacetension of the film before the corona treatment was 34 dynes/cm andimmediately after treatment was 72 dynes/cm as measured by the liquiddroplet method. Portions of the treated film were coated at roomtemperature with the following SARAN* latexes (* a tradename) and testedfor adhesion.

    ______________________________________                                        Latex       Coating Quality.sup.1                                                                      Adhesion.sup.2                                       ______________________________________                                        SL112       Good         Excellent                                            SL116       Excellent    Excellent                                            SL118       Excellent    Excellent                                            SL143       Excellent    Excellent                                            SL159       Excellent    Excellent                                            ______________________________________                                         .sup.1 Quality refers to uniformity and continuity of the coating as          visually observed.                                                            .sup.2 Adhesion was measured by sticking Scotch Tape 610* adhesive tape (     tradename) to the surface, then removing the tape; if the tape comes off      without destroying the coating, then adhesion is excellent.              

As a control, a portion of the same ECO film, not corona treated,described above could not be effectively coated with the latexes toachieve a substantial amount of adhesion.

A film of LLDPE fabricated on the same blown film line and coronatreated at the same level could not be effectively coated with thelatexes to achieve a substantial amount of adhesion.

A film of EAA (ethylene/acrylic acid) copolymer (9% AA, 9 M.I.) wassimilarly fabricated and corona treated. This film was not effectivelycoated with the latexes to achieve a substantial amount of adhesion.

EXAMPLE 8

Portions of the ECO film of Example 7 above were corona treated atlevels indicated below and the surface tension and coating quality weredetermined using SL112 and SL159.

    ______________________________________                                                        Surface**                                                     Treatment Level*                                                                              Tension   Coating Quality                                     (W/ft.sup.2 /min)                                                                       W/m.sup.2 /min.                                                                         (dynes/cm)                                                                              SL112   SL159                                   ______________________________________                                        0         0         34        Poor    Poor                                    2         21.5      50        Excellent                                                                             Excellent                               5         53.8      52        Excellent                                                                             Excellent                               ______________________________________                                         *W = watts                                                                    **measured several days after corona treatment, when effect of surface        treatment had faded somewhat.                                            

EXAMPLE 9

A 5-mil (0.125 mm) film of ECO was produced as in Example 7 above andwas corona treated at levels indicated below. The surface tension andcoating quality were determined using SL112 and SL159.

    ______________________________________                                                        Surface**                                                     Treatment Level*                                                                              Tension   Coating Quality                                     (W/ft.sup.2 /min)                                                                       W/m.sup.2 /min.                                                                         (dynes/cm)                                                                              SL112   SL159                                   ______________________________________                                        0         0         34        Poor    Poor                                    2         21.5      46        Good    DNT.sup.1                               8         86.0      53        Excellent                                                                             Excellent                               ______________________________________                                         .sup.1 DNT = did not test.                                               

EXAMPLE 10

An ethylene/vinyl acetate, EVA, 2-mil film (10% VA, 6 M.I.) was treatedwith 5 watts/ft² /min. (53.8 watts/m² /min.) corona treatment level. Thefilm had poor coating quality and had virtually no adhesion to SL112.

Within the ambit of the present invention are novel heat-sealed articleswhich serve as packaging material or coverings wherein barrierproperties are provided by the halopolymer and heat-sealability isprovided by the CO-containing polymer. In some packagings or coveringsthe heat may be applied from the exterior in those instances whereinheat-transfer to the bonding area is not impeded by the thickness ornature of the material, but heating may be more efficiently generatedfrom within the multi-ply material by the effects of high-frequencyelectromagnetic radiation, such as microwave energy, acting on theCO-containing polymer.

We claim:
 1. An article comprising a carbon monoxide-containing polymerhaving coated thereon, as an adhering layer, a halopolymer,wherein saidhalopolymer layer is one which has been applied to the carbonmonoxide-containing polymer as a fine particle aqueous dispersion orlatex and dried.
 2. The article of claim 1 wherein the carbonmonoxide-containing polymer comprises at least one selected from thegroup comprising E/CO, E/CO/VA, E/CO/MAA, and E/CO/AA.
 3. The article ofclaim 1 wherein the halopolymer comprises at least one selected from thegroup comprising polyvinylhalide, polyvinylidene halide, poly(vinylidenehalide)(vinyl halide), and halogenated polyolefins.
 4. The article ofclaim 1 wherein the halopolymer comprises a chloropolymer, afluoropolymer, or a chlorofluoropolymer.
 5. The article of claim 1wherein the carbon monoxide comprises about 1 to about 50% by weight ofthe carbon monoxide-containing polymer.
 6. The article of claim 1wherein the carbon monoxide comprises about 1 to about 40% by weight ofthe carbon monoxide-containing polymer.
 7. The article of claim 1wherein the carbon monoxide comprises about 5 to about 30% by weight ofthe carbon monoxide-containing polymer.
 8. The article of claim 1wherein the carbon monoxide-containing polymer is a film having thehalopolymer coated or adhered to one side thereof, and having adhered tothe other side thereof at least one material or substrate selected fromthe group comprising resin, paper, cloth, wood, print, adhesive, metal,ceramic, plastic, and another similar polymer.
 9. The article of claim 1wherein the fine particle aqueous dispersion or latex is one which has asolids content in the range of about 10-90% by weight.
 10. The articleof claim 1 wherein the fine particle aqueous dispersion or latex is onewhich has a solids content in the range of about 30-75% by weight. 11.The article of claim 1 wherein the fine particle aqueous dispersion oflatex is one which has a surface tension in the range of about 30-90dynes/cm.
 12. The article of claim 1 wherein the fine particle aqueousdispersion or latex is one which has a surface tension in the range ofabout 40-80 dynes/cm.
 13. The article of claim 1 wherein the surface ofthe carbon monoxide-containing polymer has been corona-treated prior tothe application of the fine particle aqueous dispersion or latex ofhalopolymer.
 14. The article of claim 3 wherein the halogenatedpolyolefin comprises halogenated polyethylene.